ACS Earth and Space Chemistry最新文献

{"title":"Reaction of the Acetyl Peroxy Radical and OH Radical as a Source of Acetic Acid in the Atmosphere","authors":"Hanhao Chen,&nbsp;Sainan Wang and Liming Wang*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0021110.1021/acsearthspacechem.4c00211","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00211https://doi.org/10.1021/acsearthspacechem.4c00211","url":null,"abstract":"<p >The potential role of the reaction between the acetyl peroxy radicals (CH₃C(O)O₂) and the hydroxyl radical in the atmosphere was investigated. Theoretical calculations show that this reaction would form acetic acid (AAc) and ¹O₂ almost exclusively. The reaction proceeds by formation of a trioxide compound as CH₃C(O)OOOH, in which rapid intramolecular hydrogen atom transfer followed by decomposition to AAc and ¹O₂ was found, while decomposition of the trioxide to CH₃CO₂ + HO₂ is negligible. With the relatively fast reaction between CH₃C(O)O₂ and OH with an estimated rate coefficient of 1.8 × 10^–10 cm³ molecule^–1 s^–1, the reaction might be a significant secondary source of AAc in the troposphere. A global atmospheric simulation using GEOS-Chem found that the title reaction results in an average increase of the mixing ratios of AAc by ∼33% (about 6.4 pptv for increase) and a net formation of about 8.0 Tg/yr AAc. Reactions between other RC(O)O₂ and OH may also contribute significantly to the formation of RC(O)OH. The atmospheric chemistry model may need to include the title reaction.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2522–2531 2522–2531"},"PeriodicalIF":2.9,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Semi-Open System Simulation of Organic-Rich Shale To Produce Organic Acids","authors":"Junxian Wang,&nbsp;Ziying Li*,&nbsp;Zilin Liu,&nbsp;Hongliang Dang,&nbsp;Jian Guo and Chuang Zhang,&nbsp;","doi":"10.1021/acsearthspacechem.4c0018710.1021/acsearthspacechem.4c00187","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00187https://doi.org/10.1021/acsearthspacechem.4c00187","url":null,"abstract":"<p >The deeply buried organic-rich black shale in basins generates a considerable amount of organic acids during thermal evolution, which is of great significance for the modification of the reservoir pore structure and the evaluation of hydrocarbon product mobility. However, research on the types of organic acids generated is still insufficient, leading to a significant underestimation of organic acid yields. In view of this, this study utilized a semi-open pyrolysis simulation device to simulate different maturity stages of organic-rich black shales through pyrolysis experiments. High-performance liquid chromatography (HPLC) was used to analyze the composition of water-soluble organic acids in the products. The results showed that the yield of organic acids was highest in the early stage of organic matter thermal maturity, reaching up to 8.58 mg/g of total organic carbon (TOC), and was rich in a variety of organic acids, mainly including quinic acid, formic acid, acetic acid, propionic acid, <i>n</i>-butyric acid, oxalic acid, lactic acid, malic acid, and tartaric acid. As thermal evolution progressed and hydrocarbons were generated in large quantities, the acid yield rapidly decreased, reaching 0.11 mg/g of TOC. Therefore, the transformative effects of acidic fluids formed by kerogen in source rocks on sandstone reservoirs can be traced back to the period before oil and gas migration. Additionally, the diversity of organic acid types has been significantly underestimated in most studies.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2420–2427 2420–2427"},"PeriodicalIF":2.9,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Determination of Rare Earth Elements in Cosmo-geological Samples Aided by Wavelength Dispersive X-ray Fluorescence Spectroscopy","authors":"Ella De Pauw*,&nbsp;Pieter Tack,&nbsp;Miles Lindner,&nbsp;Thibaut Baert,&nbsp;Jan Garrevoet,&nbsp;Dennis Brückner,&nbsp;Axel Gerdes,&nbsp;Gerald Falkenberg,&nbsp;Frank E. Brenker and Laszlo Vincze,&nbsp;","doi":"10.1021/acsearthspacechem.4c0023510.1021/acsearthspacechem.4c00235","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00235https://doi.org/10.1021/acsearthspacechem.4c00235","url":null,"abstract":"<p >While rare earth elements are generally probed with destructive techniques such as LA-ICP-MS, this causes at least partial destruction of the sample, which is not desirable when precious materials such as cosmo-geological (return) samples are examined. With the proposed wavelength dispersive synchrotron radiation X-ray fluorescence spectroscopy technique the rare earth element characteristic L-lines, situated between 4.65 and 7.66 keV, can be qualitatively and quantitatively detected in a nondestructive manner in precious samples. The method is based on a sequential scanning θ-2θ geometrical setup making use of a flat Ge(111) analyzer crystal and a small energy dispersive detector, measuring the radiation in Bragg conditions. To optimize the solid angle of detection a polycapillary half-focusing lens was positioned between the sample and the crystal, collimating and guiding the radiation. Validation of the technique is provided by comparing the obtained quantitative results with previously obtained LA-ICP-MS results measured on the sample.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2546–2556 2546–2556"},"PeriodicalIF":2.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ion Spectroscopy in the Context of the Diffuse Interstellar Bands: A Case Study with the Phenylacetylene Cation","authors":"Thomas E. Douglas-Walker,&nbsp;Ewen K. Campbell*,&nbsp;Francis C. Daly,&nbsp;Stéphane Douin,&nbsp;Bérenger Gans,&nbsp;Ugo Jacovella*,&nbsp;Colombe Maurice,&nbsp;Robin Odant and Julianna Palotás,&nbsp;","doi":"10.1021/acsearthspacechem.4c0027210.1021/acsearthspacechem.4c00272","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00272https://doi.org/10.1021/acsearthspacechem.4c00272","url":null,"abstract":"<p >Identification of the molecular carriers of diffuse interstellar bands (DIBs) requires gas phase electronic spectra of suitable candidate structures. Recording the spectra of these in the laboratory is challenging because they include large, carbon-rich molecules, many of which are likely to be ionic. The electronic spectra of ions are often obtained using action spectroscopy methods, which can induce small perturbations to the absorption characteristics and hinder comparison with astronomical observations. In this contribution, the appropriateness of helium-tagging and two-color resonant-enhanced photodissociation spectroscopy as suitable techniques to obtain the requisite laboratory data for comparison to DIBs is explored. As a proof-of-concept, the C̃ ²B₁ ← X̃ ²B₁ electronic transition of the phenylacetylene cation (PA⁺, C₈H₆⁺), obtained by helium-tagging and two-color photodissociation, is compared to the direct absorption spectrum recorded using cavity ring-down spectroscopy. The results indicate that for DIBs with typical widths of a few ångströms, the wavelengths, bandwidths, and relative intensities from action spectroscopy are obtained with sufficient precision to facilitate accurate comparisons to catalogued DIBs.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2644–2651 2644–2651"},"PeriodicalIF":2.9,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00272","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Insights into the Formation of Methyl Formate and Glycolaldehyde via Amorphous ISM Ice","authors":"Mateus Augusto Martins de Paiva,&nbsp;Breno Rodrigues Lamaghere Galvão and Heitor Avelino De Abreu*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0019010.1021/acsearthspacechem.4c00190","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00190https://doi.org/10.1021/acsearthspacechem.4c00190","url":null,"abstract":"<p >In the realm of Complex Organic Molecules (COMs) detected within the Interstellar Medium (ISM), glycolaldehyde stands out as a pivotal player due to its dual significance as the simplest sugar and a precursor of life-sustaining molecules such as ribose. Coexisting in substantial concentrations with glycolaldehyde is its isomer, methyl formate, raising questions about a potential shared formation pathway. Recent research hints at the essential role of amorphous water ice in COM formation within dense ISM nebulae. This study revisits a promising two-step pathway for glycolaldehyde synthesis, initiated by the reaction of formaldehyde with the formyl radical, followed by hydrogenation of the resulting intermediate. In addition to employing a more rigorous level of calculation, the Langmuir–Hinshelwood mechanism is explored, while also predicting the possibility of methyl formate formation from the same starting materials. Simulation efforts, using water clusters comprising 18 and 25 molecules, leverage both Density Functional Theory (DFT) and Coupled Cluster (CC) methods at distinct sites of the surface. The findings reveal that, at the DFT level, the proposed reaction leads to glycolaldehyde formation with no energy barriers, exhibiting a significant relative energy reduction of up to 129% relative to the gas-phase reaction. Conversely, at the CC level, a modest 19 kJ mol^–1 barrier is encountered at 10 K, representing a 45% reduction. We show that formation of methyl formate via this pathway is not feasible, with higher energy barriers than the primary glycolaldehyde production. Analysis of the adsorption energies suggests distinct behaviors, with glycolaldehyde intermediates remaining adsorbed until the formation of the final molecule, while methyl formate exhibits sufficient energy for desorption before the final hydrogenation step.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2442–2451 2442–2451"},"PeriodicalIF":2.9,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00190","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Understanding Titan’s Prebiotic Chemistry: Synthesizing Amino Acids Through Aminonitrile Alkaline Hydrolysis","authors":"Kendra K. Farnsworth*,&nbsp;Hannah L. McLain,&nbsp;Angela Chung and Melissa G. Trainer,&nbsp;","doi":"10.1021/acsearthspacechem.4c0011410.1021/acsearthspacechem.4c00114","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00114https://doi.org/10.1021/acsearthspacechem.4c00114","url":null,"abstract":"<p >Titan is an ocean world with a plethora of organic material in its atmosphere and on its surface, making it an intriguing location in the search for habitable environments beyond Earth. Settled aerosols will mix with transient surface melts following cryovolcanic eruptions and impact events, driving hydrolysis reactions and prebiotic chemistry. Previous studies have shown that the hydrolysis of laboratory-synthesized Titan organics leads to the production of amino acids and other prebiotic molecules. The exact molecular structure of Titan aerosols remains unclear, yet aminonitriles have been hypothesized to be among the organic components. This laboratory study tested three reaction pathways that could potentially lead to the formation of amino acids: aminoacetonitrile → glycine, 2-aminopropanenitrile → alanine, and 4-aminobutanenitrile → γ-aminobutyric acid. Liquid chromatography mass spectrometry (LCMS) is used to quantify the abundance of amino acids over a 6-month period. We conclude that ammonia plays a key role in the synthesis of amino acids from aminonitriles, while the inclusion of salts (1 wt %) and minerals (25 mg/mL) did not have a significant effect on amino acid formation compared to ammonia. Rate constants (<i>k</i>) for alkaline hydrolysis of the aminonitriles were calculated. Our results suggest that if Titan’s surface melts have a composition, including at least 5% ammonia in water, and if aminonitriles are present in Titan’s organic aerosols, then amino acids will likely form. These results are highly relevant to the Dragonfly mission to Titan, which will sample impact melt material at Selk crater to search for prebiotic molecules.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2380–2392 2380–2392"},"PeriodicalIF":2.9,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00114","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Experimental and Theoretical Investigation of the Reaction of C2H with Formaldehyde (CH2O) at Very Low Temperatures and Application to Astrochemical Models","authors":"Kevin M. Douglas*,&nbsp;Niclas A. West,&nbsp;Daniel I. Lucas,&nbsp;Marie Van de Sande,&nbsp;Mark A. Blitz and Dwayne E. Heard*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0018810.1021/acsearthspacechem.4c00188","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00188https://doi.org/10.1021/acsearthspacechem.4c00188","url":null,"abstract":"<p >Rate coefficients for the reaction of C₂H with CH₂O were measured for the first time over the temperature range of 37–603 K, with the C₂H radicals produced by pulsed laser photolysis and detected by CH radical chemiluminescence following their reaction with O₂. The low temperature measurements (≤93 K) relevant to the interstellar medium were made within a Laval nozzle gas expansion, while higher temperature measurements (≥308 K) were made within a temperature controlled reaction cell. The rate coefficients display a negative temperature dependence below 300 K, reaching (1.3 ± 0.2) × 10^–10 cm³ molecule^–1 s^–1 at 37 K, while only a slight positive temperature dependence is observed at higher temperatures above 300 K. Ab initio calculations of the potential energy surface (PES) were combined with rate theory calculations using the MESMER master-equation program in order to predict rate coefficients and branching ratios. The three lowest energy entrance channels on the PES all proceed via the initial formation of a weakly bound prereaction complex, bound by ∼5 kJ mol^–1, followed by either a submerged barrier on the route to the H-abstraction products (C₂H₂ + CHO), or emerged barriers on the routes to the C- or O-addition species. MESMER calculations indicated that over the temperature range investigated (10–600 K) the two addition channels were uncompetitive, accounting for less 0.3% of the total product yield even at 600 K. The PES containing only the H-abstraction product channel was fit to the experimentally determined rate coefficients, with only a minor adjustment to the height of the submerged barrier (from −2.6 to −5.9 kJ mol^–1) required. Using this new submerged barrier height, and including the subsequent dissociation of the CHO product into CO + H in the PES, rate coefficients and branching ratios were calculated over a wide range of temperatures and pressures and these used to recommend best-fit modified Arrhenius expressions for use in astrochemical modeling. Inclusion of the new rate coefficients and branching ratios in a UMIST chemical model of an outflow from an asymptotic giant branch (AGB) star yielded no significant changes in the abundances of the reactants or the products of the reaction, however, removal of the C-addition channel currently in the UMIST Rate22 database did result in a significant reduction in the abundance of propynal (HCCCHO).</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2428–2441 2428–2441"},"PeriodicalIF":2.9,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00188","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Charge Detection Mass Spectrometry for the Analysis of Atmospheric Dust on Mars","authors":"Elaura L. Gustafson,&nbsp;Kate E. Hales,&nbsp;Tabitha C. Caldwell,&nbsp;Halle V. Murray and Daniel E. Austin*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0011210.1021/acsearthspacechem.4c00112","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00112https://doi.org/10.1021/acsearthspacechem.4c00112","url":null,"abstract":"<p >Mars dust is a dominant feature of the planet’s atmosphere and climate, and this dust is likely charged due to natural phenomena such as dust devils and storms. Dust size is also an important characteristic as it pertains to both climatology and risk to current and future Mars exploration. Charge detection mass spectrometry (CDMS) is a technique based on both image charge detection and particle time-of-flight capable of measuring both the charge and mass of individual Mars dust grains. Measurement of these characteristics can be used to determine the particle size distribution. In this work, we report the development of a CDMS instrument made of a printed circuit board (PCB) array for the analysis of microparticles in the Martian atmosphere. Ion optic simulations show that the optimal size range for dust grains analyzed by this device is between 0.2 and 1.5 μm in diameter. Laboratory experiments using three different types of microparticles (derived from Mojave Mars Simulant-1, olivine, and chalkboard dust) show that particles having more than 1500 elementary charges of either polarity can be detected. The average particle velocity measured using time-of-flight for the olivine sample was 24.9 ± 0.4 m/s within the instrument, although different inlet designs or conditions will yield different measurement velocities.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2372–2379 2372–2379"},"PeriodicalIF":2.9,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Experimental and Theoretical Study of the OH-Initiated Degradation of Ethylenediamine (NH2CH2CH2NH2) under Simulated Atmospheric Conditions. Part 1: Kinetics of the Ethylenediamine + OH Gas Phase Reaction","authors":"Tomas Mikoviny,&nbsp;Claus J. Nielsen*,&nbsp;Armin Wisthaler and Liang Zhu,&nbsp;","doi":"10.1021/acsearthspacechem.4c0027110.1021/acsearthspacechem.4c00271","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00271https://doi.org/10.1021/acsearthspacechem.4c00271","url":null,"abstract":"<p >The ethylenediamine (NH₂CH₂CH₂NH₂) reaction with OH radicals was studied under natural sunlight conditions in a large outdoor atmospheric simulation chamber and in theoretical calculations based on CCSD(T*)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ quantum chemistry results. The OH rate coefficient was determined in relative rate experiments employing online PTR-ToF-MS detection to be <i>k</i>_OH = (2.8 ± 0.8) × 10^–10 cm³ molecule^–1 s^–1 at 308 ± 3 K and 1013 ± 3 hPa. The theoretical study includes a conformational mapping of ethylenediamine showing nine conformers to be considered in reaction kinetics modeling, CCSD(T*)-F12a/aug-cc-pVTZ optimized geometries, and results from vibrational anharmonicity calculations for all conformers. The rate coefficients for the OH radical reaction with each of the nine ethylenediamine conformers were obtained in master equation calculations showing the kinetics being governed by both the formation of prereaction adducts and by tight transition states giving a Boltzmann conformer weighted rate coefficient <i>k</i>_OH = 2.9 × 10^–10 cm³ molecule^–1 s^–1, and a 1:1 branching between H-abstraction from the NH₂ and CH₂ groups at 298 K and 1013 hPa. The calculated rate coefficient shows a negative temperature dependence and a negligible variation with pressure under atmospheric conditions. The theoretical kinetics data were aligned to the experimental result, and the rate coefficient in the 200–400 K region can be approximated by a modified Arrhenius expression <i>k</i>(T) = 1.23 × 10^–10 × (T/298)^0.6 × exp(249 K/T) cm³ molecule^–1 s^–1.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2633–2643 2633–2643"},"PeriodicalIF":2.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00271","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Insights into Gas Migration Within Ice on Earth and Icy Celestial Bodies","authors":"Yoo Soo Yi*,&nbsp; and ,&nbsp;Yeongcheol Han*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0026610.1021/acsearthspacechem.4c00266","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00266https://doi.org/10.1021/acsearthspacechem.4c00266","url":null,"abstract":"<p >Atmospheric gases trapped in icy environments, such as Earth’s polar regions and Jupiter’s moon Europa, offer a unique opportunity to explore paleoclimate and astrogeological history. While previous studies have addressed the diffusive behaviors of these gases and their implications for paleoclimatological and geochronological reconstructions, the underlying mechanisms of gas migration in ice remain largely unexplored. Achieving an atomistic-level understanding of gas migration is therefore essential for improving our knowledge of the long-term behavior of gases in icy environments. In this study, we investigated the migration of noble gases encapsulated in isolated air bubbles within bulk ice using density functional theory calculations. We focused on both the dissolution at the gas–ice interface and the subsequent molecular diffusion through the ice lattice. Our results show that energy barriers for dissolution and molecular diffusion increase almost linearly with atomic size, leading to nonlinear, exponential-like decreases in solubility and diffusivity, due to their Arrhenius behavior in relation to the corresponding energy barriers. These energy barriers primarily arise from the structural distortions in the ice lattice, as it accommodates noble gas atoms. Additionally, our findings indicate that dissolution is energetically both more demanding and slower than molecular diffusion, making it the rate-limiting step in gas migration through ice. These findings provide valuable insights into gas migration and fractionation mechanisms in Earth’s polar ice, highlighting the importance of incorporating atomic-level interactions into geochronological models. By deepening our fundamental understanding of gas mobility, this work not only advances methodologies for analyzing Earth’s ice but also broadens our perspective on extraterrestrial icy environments, with potential implications for the search for life-supporting conditions beyond Earth.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2611–2620 2611–2620"},"PeriodicalIF":2.9,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}